CN106252511A - Photo-electric conversion element and manufacture method thereof - Google Patents
Photo-electric conversion element and manufacture method thereof Download PDFInfo
- Publication number
- CN106252511A CN106252511A CN201610094609.9A CN201610094609A CN106252511A CN 106252511 A CN106252511 A CN 106252511A CN 201610094609 A CN201610094609 A CN 201610094609A CN 106252511 A CN106252511 A CN 106252511A
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- Prior art keywords
- layer
- conversion element
- photo
- organic
- electric conversion
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- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical compound CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- XJINZNWPEQMMBV-UHFFFAOYSA-N n-methylhexan-1-amine Chemical compound CCCCCCNC XJINZNWPEQMMBV-UHFFFAOYSA-N 0.000 description 1
- UOIWOHLIGKIYFE-UHFFFAOYSA-N n-methylpentan-1-amine Chemical compound CCCCCNC UOIWOHLIGKIYFE-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 description 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- GVCGWXSZNUOTDW-UHFFFAOYSA-N sulfo cyanate Chemical compound OS(=O)(=O)OC#N GVCGWXSZNUOTDW-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
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- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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Abstract
The present invention provides photoelectric transformation efficiency height, excellent in te pins of durability, the organic-inorganic mixed electrical optical conversion element of easily manufacture.Photo-electric conversion element (1) is further equipped with dense oxide titanium layer (4), porous oxidation titanium layer (5), organic-inorganic hybrid junctions crystal layer (6) and hole transmission layer (7) between the first conductive layer (3) and the second conductive layer (8), wherein, above-mentioned hole transmission layer (7) is containing the compound with following structure (I):(R1～R4The most identical or different, for hydrogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted alkyl amino, substituted or unsubstituted arylamino or substituted or unsubstituted alkoxyl (wherein, R1～R4Except being the situation of hydrogen atom), m, n, o and p are the most identical or different, are the integer of 1～5, here, in the case of the integer that any one in m, n, o and p is more than 2, corresponding R group each can be identical, it is also possible to different).
Description
Technical field
The present invention relates to the manufacture method of photo-electric conversion element and this photo-electric conversion element, relate to especially
And photoelectric transformation efficiency height, excellent in te pins of durability, the organic-inorganic mixed electrical optical conversion of easily manufacture
Element.
Background technology
Photo-electric conversion element is used for various optical sensor, photocopier, solaode etc..Special
It not that solaode is popularized the most veritably as the representative utilizing regenerative resource.As too
Sun energy battery, silicon system solaode, CIGS solaode, CdTe system solaode
Deng popularizing.
On the other hand, carry out using organic system material to replace institute in above-mentioned solaode
Inorganic based material as use is as the research of photoelectric conversion material, organic thin film solar
The exploitation of battery and dye-sensitized solar cell is carried out.Such solaode because
Vacuum technology can not be used to be manufactured by coated technique, it is possible to can significantly change
Good manufacturing cost, is expected accordingly, as follow-on solaode.
But, present situation is, above-mentioned organic thin film solar cell and dye-sensitized solar cell,
Compared with the solaode as above using inorganic based material, photoelectric transformation efficiency is the most not
Fully, durability is the lowest.
As photoelectric conversion material, there is perovskite crystalline structure in recent years it has been proposed that use
The solaode (non-patent literature 1) of lead coordination compound and electrolyte.
It addition, propose the electrolysis that will use in the solaode proposed in non-patent literature 1
Liquid replaces with 2,2 ', 7,7 '-four (N, N-dimethoxys of the organic hole transport material as solid
Phenyl amine)-9,9-spiral shell two fluorenes (2,2 ', 7,7 '-tetrakis (N, N-dimethoxyphenylamine)
-9,9 '-Spirobifluorene, hreinafter referred to as spiro-OMeTAD), and distinguish that it is changed
Efficiency is more than 10% (non-patent literature 2).
The crystallization of this use Ca-Ti ore type is as the organic nothing of what is called of the fully solid of photoelectric conversion material
Machine hybrid solar cell, exploitation develops rapidly later, and its conversion efficiency has exceeded 20%.This
The organic-inorganic hybrid solar cell of sample, in great majority are reported, employs and has following knot
The spiro-OMeTAD of structure is as hole mobile material.
It addition, on the other hand, also attempted passing in the hole of organic-inorganic hybrid solar cell
Defeated layer uses the research of inorganic material.Specifically, use Cuprous sulfocyanate as hole transport
Material, but this material has toxicity, improper accordingly, as the material for most surface layer.
Prior art literature
Patent documentation
Patent documentation 1:WO2015/016107A1
Non-patent literature
Non-patent literature 1:J.Am.Chem.Soc., 131,6050 (2009)
Non-patent literature 2:Science, 338,643 (2012)
Non-patent literature 3:J.Am.Chem.Soc.2014,136,10996
Non-patent literature 4:Chem.Commun., 2014,50,6931-6934
Summary of the invention
Invention to solve the technical problem that
Although the organic-inorganic mixed electrical optical conversion element so having good prospects, but in this institute
The hole mobile material spiro-OMeTAD used, it is difficult to synthesis, extremely expensive, therefore, become
For using photo-electric conversion element as solaode carry out large area time technical problem.
It addition, this spiro-OMeTAD is that charge transport ability is low in a neutral state, in oxidation
Just play the special material of charge transport ability under state, accordingly, there exist following problem points:
When actually used, add further in the coating liquid containing spiro-OMeTAD oxidant,
Maybe this coating liquid is placed in an atmosphere diel and makes after its air oxidation use etc., on it manufactures
Operating difficulties, after manufacture, light transfer characteristic is also difficult to control to (non-patent literature 3).
On the other hand, as hole mobile material, also used in addition to fluorenes based compound
The trial of triarylamine based compound and butadiene-based compound etc., but present situation is to be surpassed
Cross the characteristic (patent documentation 1) (non-patent literature 4) of this spiro-OMeTAD.
Therefore, it is an object of the invention to, solve above-mentioned problem of the prior art, it is provided that photoelectricity
Conversion efficiency height, excellent in te pins of durability, the organic-inorganic mixed electrical optical conversion element of easily manufacture,
It addition, other purpose of the present invention is, it is provided that can be easily manufactured photoelectric transformation efficiency high,
The manufacturer of the photo-electric conversion element of the organic-inorganic mixed electrical optical conversion element of excellent in te pins of durability
Method.
For solving the means of technical problem
The present inventor is concentrated on studies to achieve these goals, it was found that various
In the hole mobile material of various kinds, be there is by use the compound of ad hoc structure, it is possible to realize
High photoelectric transformation efficiency.This compound be as described later there is specific butadiene structure
Compound, synthesis dissolubility easily and in a solvent is the most excellent, as electrofax
The material of photoreceptor has been established for volume production technology.Therefore, it is possible to realizing high opto-electronic conversion
While efficiency, inexpensively and manufacture the solaode of large area in large quantities.
That is, the photo-electric conversion element of the present invention possesses the first conductive layer and the second conductive layer, and
Dense oxide titanium layer, porous oxygen it is further equipped with successively between first conductive layer and the second conductive layer
Change titanium layer, organic-inorganic hybrid junctions crystal layer and hole transmission layer, the feature of this photo-electric conversion element
Being, above-mentioned hole transmission layer contains the compound with following structure (I):
R1～R4The most identical or different, for hydrogen atom, substituted or unsubstituted alkyl, replacement
Or unsubstituted alkyl amino, substituted or unsubstituted arylamino or substituted or unsubstituted
Alkoxyl, wherein, R1～R4Except being the situation of hydrogen atom, m, n, o are the most identical with p
Or different, be the integer of 1～5, here, any one in m, n, o and p be more than 2 whole
In the case of number, corresponding R group each can be identical, it is also possible to different.
In the preference of the photo-electric conversion element of the present invention, in said structure (I), R1With
R2For-p-N-Et2, R3And R4For hydrogen atom.
In other preference of the photo-electric conversion element of the present invention, above-mentioned organic-inorganic hybrid junctions
Crystal layer is by CH3NH3PbX3The Ca-Ti ore type crystallization structure that (wherein, X is halogen atom) represents
The layer become.
In other preference of the photo-electric conversion element of the present invention, notationally state Ca-Ti ore type
Formula CH of crystallization3NH3PbX3In, X is atomic iodine.
It addition, the manufacture method of the photo-electric conversion element of the present invention is above-mentioned photo-electric conversion element
Manufacture method, it is characterised in that above-mentioned hole transmission layer is by making have said structure (I)
Compound dissolution prepare coating liquid in organic solvent, this coating liquid is coated in organic-inorganic
On hybrid junctions crystal layer, then remove organic solvent and formed.
Invention effect
Photo-electric conversion element according to the present invention, using the teaching of the invention it is possible to provide photoelectric transformation efficiency is high, durability
Organic-inorganic mixed electrical optical conversion element excellent, that easily manufacture.
The manufacture method of the photo-electric conversion element according to the present invention, using the teaching of the invention it is possible to provide can easily make
Make the photoelectricity of the organic-inorganic mixed electrical optical conversion element of photoelectric transformation efficiency height, excellent in te pins of durability
The manufacture method of conversion element.
Accompanying drawing explanation
Fig. 1 is the sectional view of an example of the photo-electric conversion element schematically showing the present invention.
Symbol description
1 photo-electric conversion element
2 substrates
3 first conductive layers
4 dense oxide titanium layers
5 porous oxidation titanium layers
6 organic-inorganic hybrid junctions crystal layers
7 hole transmission layers
8 second conductive layers
Detailed description of the invention
Hereinafter, photo-electric conversion element and the manufacture method thereof of the present invention is described in detail with reference to Fig. 1.Figure
1 is an example (the first embodiment) of the photo-electric conversion element schematically showing the present invention
Sectional view.Photo-electric conversion element 1 shown in Fig. 1 possesses the first conductive layer 3 as negative electrode and makees
For the second conductive layer 8 of anode, it is further equipped with between the first conductive layer 3 and the second conductive layer 8
Dense oxide titanium layer 4, porous oxidation titanium layer 5, organic-inorganic hybrid junctions crystal layer 6 and hole transmission layer
7.Photo-electric conversion element 1 shown in Fig. 1, photoelectric conversion layer is organic-inorganic hybrid junctions crystal layer 6,
It is referred to as organic-inorganic mixed electrical optical conversion element.
The photo-electric conversion element needs of the present invention possess between the first conductive layer and the second conductive layer
Dense oxide titanium layer, porous oxidation titanium layer, organic-inorganic hybrid junctions crystal layer and hole transmission layer,
Preferably from as the first conductive layer of negative electrode according to dense oxide titanium layer, porous oxidation titanium layer,
Organic-inorganic hybrid junctions crystal layer, the order of hole transmission layer carry out stacking.Specifically, such as light
Shown in electric transition element 1, on the first conductive layer 3, preferably form dense oxide titanium layer 4, in this cause
Form porous oxidation titanium layer 5 on close titanium oxide layer 4, this porous oxidation titanium layer 5 forms organic nothing
Machine hybrid junctions crystal layer 6, forms hole transmission layer 7, at this on this organic-inorganic hybrid junctions crystal layer 6
The second conductive layer 8 is formed on hole transmission layer 7.
The photo-electric conversion element of the present invention, as it is shown in figure 1, substrate 2 can be further equipped with,
In the case of Gai, the preferably first conductive layer 3 be formed on a substrate 2.It addition, as shown in Figure 1 from base
Plate 2 side is irradiated in the case of light, preferably makes substrate 2 for transparency carrier, makes the first conductive layer 3 be
Prescribed electrode, but in the case of irradiating light from the second conductive layer 8 side, preferably make the second conductive layer
8 is transparency electrode.Both the first conductive layer 3 and the second conductive layer 8 can also be made for transparency electrode.
1. the first conductive layer
First conductive layer is the layer that the negative electrode as photo-electric conversion element plays a role, as can
For the cathode material of this first conductive layer, such as, can enumerate: Copper diiodide (CuI), indium stannum
Oxide (ITO), stannum oxide (SnO2), fluorine doped tin oxide (FTO), Al-Doped ZnO
(AZO), the conductive clear material such as indium-zinc oxide (IZO), gallium-doped zinc oxide (GZO)
Material, sodium, sodium-potassium-sodium alloy, lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, aluminum-
Lithium alloy, aluminum-aluminium oxide (Al/Al2O3) mixture, aluminum-lithium fluoride (Al/LiF) mixture
Deng.These materials can be used alone, it is also possible to and use two or more.
First conductive layer such as can form the moon by utilizing the usual ways such as evaporation on substrate
The film of pole material manufactures.In the photo-electric conversion element of the present invention, substrate is not particularly limited,
Such as can enumerate the transparent glass substrate such as soda-lime glass, alkali-free glass, ceramic substrate, transparent
Plastic base etc., it is possible to suitably use commercially available product.
The thickness of the first conductive layer is preferably the scope of 0.4～1.5 μm.When the thickness of conductive layer is less than
During 0.4 μm, it is difficult to obtain sufficient electric conductivity.On the other hand, exceed when the thickness of conductive layer
During 1.5 μm, transmitance reduces, and photoelectric transformation efficiency is easily reduced.
2. dense oxide titanium layer
Dense oxide titanium layer constitutes electronics receiving layer together with porous oxidation titanium layer described later, fine and close
Titanium oxide layer has the first conductive layer and the second conductive layer preventing the reason as electromotive force reduction
The effect of contact.In the present invention, compacted zone refer to space few and later stacking photoelectricity turn
During conversion materials, photoelectric conversion material will not infiltrate the layer of (infiltration), porous layer refer to space big,
Photoelectric conversion material can infiltrate (infiltration) and have the layer of the long-pending effect of enlarged surface.
The thickness of dense oxide titanium layer is preferably 5～200nm, and more preferably 10～100nm.
Dense oxide titanium layer such as can be by operating formation as follows: preparation is containing titanium chelate compounds
The coating liquid of thing, utilizes spin-coating method, silk screen print method, spray pyrolysis, aerosol deposition method
Deng film-forming method, coating liquid is coated on the first conductive layer, is then fired.It addition,
After forming dense oxide titanium layer, dense oxide titanium layer can be immersed in the aqueous solution of titanium tetrachloride
In, thereby, it is possible to increase the compactness of dense oxide titanium layer.
Titanium chelate compound as the formation that can be used in dense oxide titanium layer, it is possible to use
The commercially available products such as TYZOR (registered trade mark) the AA series that DuPont manufactures, preferably have second
The compound of ethyl sodio acetoacetic ester chelation group or there is the compound of beta-diketon chelation group.
Titanium chelate compound as the formation that can be used in dense oxide titanium layer has acetyl second
The compound of acid esters chelation group, can enumerate:
Double (methyl acetoacetate) metatitanic acid diisopropyl ester,
Double (ethyl acetoacetate) metatitanic acid diisopropyl ester,
Double (propyl acetoacetate) metatitanic acid diisopropyl ester,
Double (butyl-acetoacetate) metatitanic acid diisopropyl ester,
Double (methyl acetoacetate) dibutyltitanate,
Double (ethyl acetoacetate) dibutyltitanate,
(methyl acetoacetate) metatitanic acid three isopropyl ester,
(ethyl acetoacetate) metatitanic acid three isopropyl ester,
(methyl acetoacetate) metatitanic acid tributyl,
(ethyl acetoacetate) metatitanic acid tributyl,
Three (methyl acetoacetate) isopropyl titanate,
Three (ethyl acetoacetate) isopropyl titanate,
Three (methyl acetoacetate) iso-butyl titanate,
Three (ethyl acetoacetate) iso-butyl titanate etc.,
As having the compound of beta-diketon chelation group, can enumerate:
Double (acetylacetone,2,4-pentanedione) titanium of diisopropoxy,
Diisopropoxy double (acid of 2,4-heptadione) titanium,
Double (acetylacetone,2,4-pentanedione) titanium of dibutoxy,
Dibutoxy double (acid of 2,4-heptadione) titanium,
Three isopropoxies (acetylacetone,2,4-pentanedione) titanium,
Three isopropoxies (acid of 2,4-heptadione) titanium,
Three butoxy (acetylacetone,2,4-pentanedione) titanium,
Three butoxy (acid of 2,4-heptadione) titanium,
Isopropoxy tri acetylacetonato titanium,
Isopropoxy three (acid of 2,4-heptadione) titanium,
Isobutoxy tri acetylacetonato titanium,
Isobutoxy three (2,4-heptadione acid) titanium etc., but it is not limited to these.
3. porous oxidation titanium layer
Porous oxidation titanium layer constitutes electronics receiving layer together with dense oxide titanium layer, by organic nothing
Machine mixed crystallization or hole mobile material (hole transferring agent) enter the pore of porous layer, have
The surface area with organic-inorganic hybrid junctions crystal layer or the interface of hole transmission layer is made to increase, make generation
The quantity of electric charge increase effect.
The thickness of porous oxidation titanium layer is preferably 100～20000nm, more preferably 200～
1500nm。
Porous oxidation titanium layer such as can be by operating formation as follows: preparation is containing titan oxide particles
Coating liquid, utilize spin-coating method, silk screen print method, spray pyrolysis, aerosol deposition method etc.
Coating liquid is coated on dense oxide titanium layer by film-forming method, is then fired.It addition,
Containing in the case of organic bond in above-mentioned coating liquid, needs make organic viscous by firing process
Mixture disappears.
There is several crystal formation in titanium oxide, but the formation of porous oxidation titanium layer is preferably used anatase
The titan oxide particles of type.
Coating liquid for the formation of porous oxidation titanium layer such as can be by by titan oxide particles
(P-25 etc. that Aerosil Co., Ltd. of Japan manufactures) is dispersed in alcohol (ethanol etc.) or will
Alcohol (ethanol etc.) used by titanium oxide cream (PST-18NR etc. that RiHui catalyst synthesis Co., Ltd manufactures)
Prepared by dilution.
As can be used in the organic bond of above-mentioned coating liquid, it is not particularly limited, preferably second
Base cellulose or acrylic resin.The low-temperature decomposition of acrylic resin is excellent, even if carrying out
In the case of low-firing, organic detritus amount is also few, the most particularly preferably.Acrylic resin is preferred
The acrylic resin decomposed in a low temperature of about 300 DEG C, such as can suitably use will be selected from (first
Base) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate, (first
Base) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) Isobutyl 2-propenoate,
(methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) propylene
Acid isobornyl thiocyanoacetate, (methyl) n-stearyla crylate, (methyl) benzyl acrylate and having
At least one (methyl) acrylic monomers in (methyl) acrylic monomers of polyoxyalkylene structure
The polymer being polymerized.
The pore diameter of porous oxidation titanium layer can be by changing the particle diameter or organic of titan oxide particles
Kind or the addition of binding agent adjust.
4. organic-inorganic hybrid junctions crystal layer
Organic-inorganic hybrid junctions crystal layer is the photoelectric conversion layer being made up of organic-inorganic mixed crystallization,
Absorbing light and generate electric charge.Organic-inorganic hybrid junctions crystal layer is because having the property being derived from inorganic material
Matter, so, with compared with the photoelectric conversion layer that organic material is constituted, durability is high.Preferably have
Machine inorganic hybrid junctions crystal layer is to be crystallized, by Ca-Ti ore type, the layer constituted.Ca-Ti ore type crystalline texture
Ultimate unit lattice is as shown below.
As represent at this, it is possible to the Ca-Ti ore type for organic-inorganic hybrid junctions crystal layer is tied
Crystalline substance has the ultimate unit lattice of cubic system, and each apex configuration at cubic crystal has organic group
A, is configured with metal B in body-centered, and each center of area at the cubic crystal centered by metal B is configured with
Halogen X, by formula A-B-X3Represent.
At formula A-B-X3In, as the concrete example of organic group A, methylamine, second can be enumerated
Amine, propylamine, butylamine, amylamine, hexylamine, dimethylamine, diethylamine, di-n-propylamine, dibutyl amine,
Diamylamine, dihexylamine, trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, triamylamine, three oneself
Amine, ethylmethylamine, methyl-propyl amine, butyl methyl amine, methyl amyl amine, hexyl methyl
Amine, ethyl propyl amine, N-Ethylbutylamine, imidazoles, azoles, pyrroles, aziridine, nitrogen purine, nitrogen
Azetidine, azete, azoles, imidazoline, carbazole and their ion (such as ammonium methyl (CH3NH3)
Deng) or phenethyl ammonium etc..Wherein, preferably methylamine, ethamine, propylamine, butylamine, amylamine, oneself
Amine and their ion or phenethyl ammonium, more preferably methylamine, ethamine, propylamine and their ion
(such as ammonium methyl (CH3NH3) etc.).
At formula A-B-X3In, as the concrete example of metal B, can enumerate lead, stannum, zinc,
Titanium, antimony, bismuth, nickel, ferrum, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese,
Chromium, molybdenum, europium etc..Wherein, when metal B is lead, the characteristic of organic-inorganic hybrid junctions crystal layer is good
Good.It addition, these elements can be used alone, it is also possible to and use two or more.
At formula A-B-X3In, halogen X is chlorine, bromine or iodine, and these elements can be used alone,
And can also be used two or more.Wherein, from the standpoint of band gap narrows, preferably at least the 1 of X
Individual for iodine.
In the photo-electric conversion element of the present invention, preferably organic-inorganic hybrid junctions crystal layer is served as reasons
CH3NH3PbX3The layer that the Ca-Ti ore type crystallization that (wherein, X is halogen atom) represents is constituted,
In formula CH representing the crystallization of this Ca-Ti ore type3NH3PbX3In, further preferred X is atomic iodine.
The Ca-Ti ore type crystallization that can use as organic-inorganic hybrid junctions crystal layer, it is possible to by making
With AX and BX2Synthesize as raw material.It is known that have by by AX solution and BX2
Solution is mixed and heated stirring and synthesizes 1 terrace work of Ca-Ti ore type crystallization, and by BX2Solution is coated with
Apply formation coated film on such as porous oxidation titanium layer, this coated film applies AX solution, makes
BX2Reacting with AX, thus 2 terrace works etc. of synthesis Ca-Ti ore type crystallization, either method all can
For the formation of organic-inorganic hybrid junctions crystal layer, as coating method, it is not particularly limited, can
To enumerate spin-coating method, silk screen print method, dip coating method etc..
5. hole transmission layer
Hole transmission layer is to catch the hole produced in organic-inorganic hybrid junctions crystal layer and make it migrate
Layer to the second conductive layer as anode.The photo-electric conversion element of the present invention is characterised by,
Hole transmission layer comprises the compound with following structure (I):
(R1～R4The most identical or different, for hydrogen atom, substituted or unsubstituted alkyl, replacement or
Unsubstituted alkyl amino, substituted or unsubstituted arylamino or substituted or unsubstituted alkane
Epoxide (wherein, R1～R4Except being the situation of hydrogen atom), m, n, o are the most identical with p
Or different, be the integer of 1～5, here, any one in m, n, o and p be more than 2 whole
In the case of number, corresponding R group each can be identical, it is also possible to different).By making apparatus
There is the compound of said structure (I) as hole mobile material, it is possible to realize high opto-electronic conversion
Efficiency.
In said structure (I), R1～R4The most identical or different, for hydrogen atom, replacement or not
Substituted alkyl, substituted or unsubstituted alkyl amino, substituted or unsubstituted arylamino or
The substituted or unsubstituted alkoxyl of person, here, R1～R4Except being the situation of hydrogen atom.Make
For substituted or unsubstituted alkyl, such as, can enumerate methyl (Me), ethyl (Et) etc.,
Alternatively or unsubstituted alkyl amino, dimethylamino (NMe can such as be enumerated2)、
Diethylamino (NEt2), dipropylamino (NPr2) etc., alternatively or unsubstituted virtue
Base amino, such as, can enumerate dibenzyl amino (NBenzyl2) etc., alternatively or do not take
The alkoxyl in generation, such as, can enumerate methoxyl group (OMe) etc..
In said structure (I), m, n, o and p are the most identical or different, are the integer of 1～5,
Here, in the case of the integer that any one is more than 2 in m, n, o and p, corresponding R base
Group each can be identical, it is also possible to different.Such as in the case of m is 2, at said structure (I)
Middle existence 2 is as the R of corresponding R group1, these R1Can be identical, it is also possible to different.Excellent
M, n, o and p is selected to be 1.
It is shown in having the concrete example of compound of said structure (I), i.e. exemplary compounds 1～13
Table 1.It addition, in Table 1, " p " record and represent at the phenyl ring being bonded with butadiene structure
On the Position Number of carbon atom when being set to 1, substituent R is positioned at the carbon that Position Number is 4 of phenyl ring
On atom.
[table 1]
| Numbering | R1 | R2 | R3 | R4 |
| 1 | -p-NEt2 | -p-NEt2 | -H | -H |
| 2 | -p-NBenzyl2 | -p-NMe2 | -H | -H |
| 3 | -p-NBenzyl2 | -p-NEt2 | -H | -H |
| 4 | -p-NBenzyl2 | -p-NPr2 | -H | -H |
| 5 | -p-NEt2 | -H | -Me | -Me |
| 6 | -p-NEt2 | -H | -H | -H |
| 7 | -p-NMe2 | -p-NMe2 | -H | -H |
| 8 | -p-NMe2 | -H | -H | -H |
| 9 | -p-NMe2 | -H | -p-Me | -p-Me |
| 10 | -p-NPr2 | -p-NPr2 | -H | -H |
| 11 | -p-NPr2 | -H | -H | -H |
| 12 | -p-NEt2 | -p-NEt2 | -p-OMe | -p-OMe |
| 13 | -p-NEt2 | -p-NEt2 | -p-Et | -p-Et |
In the photo-electric conversion element of the present invention, the compound with said structure (I) preferably exists
R in structure (I)1And R2For-p-N-Et2、R3And R4For the compound of hydrogen atom, particularly preferably
Exemplary compounds 1 in exemplary compounds shown in table 1.
The compound with said structure (I) such as can pass through Japanese Laid-Open Patent Publication 62-30255
Method described in publication etc. synthesizes, it is possible to suitably use commercially available product.
Hole transmission layer can be by operating formation as follows: makes the chemical combination with said structure (I)
Thing is dissolved in organic solvent (such as chlorobenzene etc.) prepares coating liquid, is coated in by this coating liquid
On organic-inorganic hybrid junctions crystal layer, then remove organic solvent.Coating method is not particularly limited,
Spin-coating method, silk screen print method, dip coating method etc. can be enumerated.The photoelectric conversion element of the present invention
The manufacture method of part comprises the formation process of such hole transmission layer, therefore, it is possible to easily
Manufacture photoelectric transformation efficiency height, the organic-inorganic mixed electrical optical conversion element of excellent in te pins of durability, energy
Enough it is suitable for the manufacture of large-area photovoltaic power generation system.It addition, the photoelectricity of the present invention turns
The manufacture method changing element can use cheap material, thus, it is also possible to cut down cost.
The thickness of hole transmission layer is preferably 20～500nm, and more preferably 50～150nm.
It addition, the compound with said structure (I) is the compound being difficult to occur crystallization, but,
In order to be more reliably prevented from the crystallization with the compound of said structure (I), hole transmission layer
Organic bond resin, plasticizer etc. can be contained.
6. the second conductive layer
Second conductive layer is the layer that the anode as photo-electric conversion element plays a role, as can
For the anode material of this second conductive layer, it is not particularly limited, it is possible to use known
Material, such as, can enumerate: the metal such as gold, silver, platinum, Copper diiodide (CuI), indium stannum aoxidize
Thing (ITO), stannum oxide (SnO2), fluorine doped tin oxide (FTO), Al-Doped ZnO (AZO),
Conductive clear material, the electric conductivity such as indium-zinc oxide (IZO), gallium-doped zinc oxide (GZO)
Transparent polymer etc..These materials can be used alone, it is also possible to and use two or more.
Second conductive layer such as can be by utilizing the usual ways such as evaporation on hole transmission layer
The film forming anode material manufactures.In the case of gold electrodes, the thickness of the second conductive layer is excellent
Elect 50nm～100nm as.
[embodiment]
Hereinafter, enumerate embodiment and the present invention is described in further detail, but the present invention is not subject to
Any restriction of following embodiment.
(embodiment 1)
1. the first conductive layer
Prepare evaporation and have the SnO being doped with fluorine2The glass substrate (thickness 2.2mm) of conducting film,
Cut into the size of 25mm × 25mm.Carry out 1 hour ultrasonic waves for cleaning, then, carry out 30 points
Clock UV light irradiates.
2. dense oxide titanium layer
First, by double for diisopropoxy (acetylacetone,2,4-pentanedione) titanium (Titanium (IV) bis
(acetylacetonate) diisopropoxide) 75 mass %1-butanol solutions
(manufacture of Sigma-Aldrich company) dilutes with n-butyl alcohol, prepares the concentration of titanium chelate compound
Dense oxide titanium layer solution (coating liquid) for 0.02mol/L.Then, spin-coating method is utilized to exist
Above-mentioned dense oxide titanium layer is applied with molten on the first conductive layer made in " 1. the first conductive layer "
Liquid, heats overlay 15 minutes at 450 DEG C, forms the dense oxide titanium layer of thickness 50nm.
3. porous oxidation titanium layer
First, by the alcohol dispersion liquid (waving the PST-18NR that catalyst chemical conversion manufactures day) of titanium oxide
1g ethanol 2.5g dilutes, and prepares porous oxidation titanium layer coating liquid.Then, spin-coating method is utilized to exist
Above-mentioned porous oxidation titanium layer is applied on the dense oxide titanium layer made in " 2. dense oxide titanium layer "
With coating liquid, it is fired, forms the porous oxidation titanium layer of thickness 300nm.Firing condition is
450 DEG C 1 hour.
4. organic-inorganic mixed layer
First, PbCl is made2(Tokyo chemical conversion manufactures) 1.4g heating for dissolving is at N, N-dimethyl formyl
In amine (DMF) 3ml, make coating liquid.Utilize spin-coating method at " 3. porous oxidation titanium layer "
Apply this coating liquid on the porous oxidation titanium layer of middle making, make coated film.The color of coated film
For the yellow identical with the color of coating liquid.
Then, CH is made3NH3I (manufacturing with Guang Chun medicine Co., Ltd.) 0.4g is dissolved in isopropanol 40ml
In, beaker is filled this solution.PbCl is possessed by make before2The glass plate of coated film
It is immersed in CH3NH3In the solution of I.Coated film becomes black from yellow immediately, can confirm that formation
By CH3NH3PbI3The Ca-Ti ore type crystallization represented.So define organic nothing by 2 terrace works
Machine mixed layer.
5. hole transmission layer
Make as hole mobile material by following formula:
Exemplary compounds 1 in the table 1 represented (T-405 that STOL spice Co., Ltd. manufactures) 60mg
It is dissolved in chlorobenzene 2ml, prepares hole transmission layer solution (coating liquid).Spin-coating method is utilized to exist
This solution is applied on the organic-inorganic mixed layer made in " 4. organic-inorganic mixed layer ", then,
Make coated film heat drying remove organic solvent, form the hole transmission layer of thickness 100nm.
6. the second conductive layer
Vacuum evaporation is utilized on the hole transmission layer of making, to form face in " 5. hole transmission layer "
Long-pending 5mm × 5mm, thickness 100nm gold evaporation film as anode, produce having of embodiment 1
Machine inorganic mixed electrical optical conversion element.
7. the mensuration of photoelectric transformation efficiency
Using the gold evaporation film of organic-inorganic mixed electrical optical conversion element that makes as anode, with
FTO evaporation film, as negative electrode, uses 25mW/cm2The white light source of light intensity
It is interelectrode that (the COLD LIGHT HL150 that HOYA-SCHOTT company manufactures) measures two
Photoelectromotive force, photoelectric current, measure the photoelectric transformation efficiency of organic-inorganic mixed electrical optical conversion element.
Its result, photoelectric transformation efficiency is 10.1%.
(embodiment 2)
Exemplary compounds 3 is used to replace exemplary compounds 1, in addition, similarly to Example 1
Operation, obtains the organic-inorganic mixed electrical optical conversion element of embodiment 2.Photoelectric transformation efficiency is
8.4%.
(embodiment 3)
Exemplary compounds 4 is used to replace exemplary compounds 1, in addition, similarly to Example 1
Operation, obtains the organic-inorganic mixed electrical optical conversion element of embodiment 3.Photoelectric transformation efficiency is
8.6%.
(comparative example 1)
Make hole transmission layer as described below, in addition, operate similarly to Example 1,
Obtain the organic-inorganic mixed electrical optical conversion element of comparative example 1.Photoelectric transformation efficiency is 7.4%.
Using spiro-OMeTAD (the Luminescence Technology as hole mobile material
Company manufactures) 144mg, double (fluoroforms as ion conductive material (ionic conductive agent)
Sulphonyl) imine lithium (lithium bis (trifluoromethanesulfonyl) imide) (bank field
Learn Co., Ltd. (Kishida Chemical Co., Ltd.) to manufacture) 18mg and 4-tert-butyl group pyrrole
Pyridine (Tokyo HuaCheng Industry Co., Ltd's manufacture) 53mg is dissolved in chlorobenzene (bank field chemistry strain formula meeting
Society manufactures) in 2ml, prepare hole transmission layer coating liquid.In order to make spiro-OMeTAD oxygen
Change, hole transmission layer coating liquid is placed 1 day in atmosphere.Then, spin-coating method is utilized to have
Apply hole transmission layer coating liquid on the inorganic mixed layer of machine, then, make coated film heat drying
And remove organic solvent, form the hole transmission layer of thickness 100nm.
(comparative example 2)
Use has a structure in which
Hole mobile material replace exemplary compounds 1, in addition, operate similarly to Example 1,
Obtain the organic-inorganic mixed electrical optical conversion element of comparative example 2.It addition, organic nothing of comparative example 2
Machine mixed electrical optical conversion element, after coating hole transmission layer coating liquid, hole mobile material
There is crystallization, it is impossible to measure photoelectric transformation efficiency.
Industrial applicability
The photo-electric conversion element of the present invention can be suitable for solaode, using the teaching of the invention it is possible to provide photoelectricity
Conversion efficiency height, excellent in te pins of durability, the organic-inorganic mixed electrical optical conversion element of easily manufacture,
Therefore, it is possible to be particularly suitable for large-area photovoltaic power generation system (megawatt solar energy (Mega
) and the power supply of small portable device Solar).
Claims (5)
1. a photo-electric conversion element, it possesses the first conductive layer and the second conductive layer, and
Dense oxide titanium layer, porous oxidation it is further equipped with successively between one conductive layer and the second conductive layer
Titanium layer, organic-inorganic hybrid junctions crystal layer and hole transmission layer, the feature of described photo-electric conversion element
It is:
Described hole transmission layer contains the compound with following structure (I):
R1～R4The most identical or different, for hydrogen atom, substituted or unsubstituted alkyl, replacement or not
Substituted alkyl amino, substituted or unsubstituted arylamino or substituted or unsubstituted alcoxyl
Base, wherein, R1～R4Except being the situation of hydrogen atom, m, n, o are the most identical with p or not
With, it is the integer of 1～5, here, the integer that any one in m, n, o and p is more than 2
In the case of, corresponding R group each can be identical, it is also possible to different.
Photo-electric conversion element the most according to claim 1, it is characterised in that:
In described structure (I), R1And R2For-p-N-Et2, R3And R4For hydrogen atom.
Photo-electric conversion element the most according to claim 1 and 2, it is characterised in that:
Described organic-inorganic hybrid junctions crystal layer is by CH3NH3PbX3The Ca-Ti ore type crystallization represented
The layer constituted, wherein, X is halogen atom.
Photo-electric conversion element the most according to claim 3, it is characterised in that:
In formula CH representing the crystallization of described Ca-Ti ore type3NH3PbX3In, X is atomic iodine.
5. a manufacture method for photo-electric conversion element, it is institute any one of Claims 1 to 4
The manufacture method of the photo-electric conversion element stated, the feature of the manufacture method of described photo-electric conversion element
It is:
Described hole transmission layer is by making the compound dissolution with described structure (I) organic molten
Agent is prepared coating liquid, this coating liquid is coated on organic-inorganic hybrid junctions crystal layer, then removes
Organic solvent is gone to be formed.
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| CN110473966A (en) * | 2018-05-09 | 2019-11-19 | 夏普株式会社 | The manufacturing method of photo-electric conversion element |
| CN110754004A (en) * | 2017-05-05 | 2020-02-04 | 洛桑联邦理工学院 | Inorganic hole conductor-based perovskite photoelectric conversion device having high operational stability for a long period of time |
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| EP4300815A1 (en) * | 2022-06-30 | 2024-01-03 | Sociedad Anónima Minera Catalano-Aragonesa | Photovoltaic panel on ceramic support |
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| CN1983039A (en) * | 2005-12-15 | 2007-06-20 | 夏普株式会社 | Method for producing electrophotographic photoreceptor, electrophotographic photoreceptor and image forming apparatus |
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| US5192633A (en) * | 1989-05-09 | 1993-03-09 | Mita Industrial Co., Ltd. | Laminate type photosensitive material for electrophotography |
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| JP5471352B2 (en) * | 2009-11-24 | 2014-04-16 | コニカミノルタ株式会社 | Photoelectric conversion element and solar cell |
| EP3413365B1 (en) * | 2012-09-18 | 2022-06-29 | Oxford University Innovation Limited | Optoelectronic device |
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| CN1983039A (en) * | 2005-12-15 | 2007-06-20 | 夏普株式会社 | Method for producing electrophotographic photoreceptor, electrophotographic photoreceptor and image forming apparatus |
| WO2014132076A1 (en) * | 2013-03-01 | 2014-09-04 | Isis Innovation Limited | Semiconducting layer production process |
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| CN110754004A (en) * | 2017-05-05 | 2020-02-04 | 洛桑联邦理工学院 | Inorganic hole conductor-based perovskite photoelectric conversion device having high operational stability for a long period of time |
| CN108376745A (en) * | 2018-03-01 | 2018-08-07 | 京东方科技集团股份有限公司 | Light emitting diode with quantum dots and preparation method thereof, display panel |
| CN110473966A (en) * | 2018-05-09 | 2019-11-19 | 夏普株式会社 | The manufacturing method of photo-electric conversion element |
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